DE3811012A1 - ORTHO SUBSTITUTED PHENOLETHERS AND FUNGICIDES THAT CONTAIN THESE COMPOUNDS - Google Patents

Abstract

Ortho-substituted phenol ethers of the general formula I <IMAGE> I where R1is C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or amino which is unsubstituted or mono- or disubstituted by C1-C4-alkyl, R2 is C1-C4-alkyl, R3 is aryloxy, arylthio or arylalkoxy, the aromatic ring being unsubstituted or substituted by one or more of the following radicals: halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-alkylthio, C1-C2-haloalkyl, aryl, aryl-C1-C2-alkoxy, C1-C4-alkylcarbonyl, mono- or di-C1-C4-alkylsubstituted amino, cyano, nitro, X is CH or N, and Y is saturated or unsaturated C2-C12-alkylene, and fungicides containing these compounds.

Description

The present invention relates to valuable new ortho-substituted ones Phenol ethers with fungicidal activity and fungicides which these compounds contain.

It is known to use acrylic acid methyl esters, e.g. B. the α - (2-benzyloxyphenyl- β -methoxyacrylic acid methyl ester (DE-35 19 282.8) or the α - (2-phenoxy-methylenephenyl) - β- methoxyacrylic acid methyl ester (DE-35 45 319.2) as fungicides. Their fungicidal action however, is unsatisfactory.

It has been found that ortho-substituted phenol ethers of the general Formula I.

in the

R¹ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or optionally mono- or doubly substituted amino by C₁-C₄-alkyl,
R² is C₁-C₄-alkyl,
R³ means aryloxy, arylthio or arylalkoxy, the aromatic ring optionally being substituted by one or more of the following radicals: halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-alkylthio, C₁-C₂-haloalkyl, aryl , Aryl-C₁-C₂-alkoxy, C₁-C₄-alkylcarbonyl, amino or cyano, nitro mono- or doubly substituted by C₁-C₄-alkyl,
X represents CH or N,
Y represents an optionally unsaturated C₂-C₁₂ alkylene radical,

have an excellent fungicidal activity that is better than that well-known acrylic acid methyl ester.  

The radicals listed in the general formula can, for example have the following meaning:

R1 can e.g. B. optionally branched C₁-C₄ alkyl (e.g. methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl), C₁-C₄ alkoxy (e.g. Methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec.- or tert.-butoxy), C₁-C₄-alkylthio (e.g. methylthio, ethylthio, n- or iso-propylthio, n -, Iso-, sec- or tert-butylthio), optionally mono- or doubly substituted amino (e.g. amino, methylamino, dimethylamino, diethylamino, diisopropylamino) by C₁-C₄alkyl.
R² can e.g. B. C₁-C₄ alkyl (z. B. methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl).
R³ can e.g. B. Aryloxy (phenoxy, 1-naphthyloxy, 2-naphthyloxy), arylthio (phenylthio) or aryloxy (benzyloxy), where the aromatic ring may optionally be substituted by one or more of the following radicals:
Halogen, (e.g. fluorine, chlorine, bromine), C₁-C₆-alkyl (e.g. methyl, ethyl, n- or iso-propyl, n-, iso-, sec.- or tert.-butyl, n-, iso-, sec.-, tert.- or neo-pentyl, hexyl), C₁-C₆-alkoxy (e.g. methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec. - or tert.-butoxy), C₁-C Alkyl-alkylthio (e.g. methylthio, ethylthio), C₁-C₂-haloalkyl (e.g. difluoromethyl, trifluoromethyl, aryl (e.g. phenyl), aryl-C₁- C₂-alkoxy (e.g. benzyloxy), C₁-C₄-alkylcarbonyl (e.g. acetyl), with C₁-C₄-alkyl mono- or doubly substituted amino (e.g. dimethylamino), cyano, nitro.

The radical X listed in the general formula I can be CH or N mean,

Y can e.g. B. mean: a straight-chain C₂-C₁₂ alkylene radical (z. B. Ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, Nonylen, decylene), a branched C₂-C₁₂ alkylene radical (e.g. Methylethylene), a C₄-C₁₂ alkylene radical (e.g. butenylene).

The new compounds can, for example, by the following methods getting produced:

The representation of the compounds of general formula Ia (R¹ = alkoxy, X = CH, R², R³ and Y have the meaning given above). B. by reaction of the ortho-substituted phenylacetic esters of the general  Formula III with methyl formate using a base (e.g. Sodium hydride) in an inert solvent such as. B. diethyl ether or Tetrahydrofuran (see also Ann. Chem. 424 [1921] 214). The so obtained Hydroxymethylene derivatives of the general formula IV, which are also in equilibrium with the formyl derivatives V can be with a Alkylating agents (e.g. dimethyl sulfate) in the presence of a base (e.g. Potassium carbonate) in a diluent (e.g. acetone) for the reaction brought. In the following formula pictures "Alk" means a C₁-C₄-alkyl- group and L a leaving group (e.g. methyl sulfate).

To prepare the compounds of the general formula Ib (R¹ = alkylthio, X = CH, R², R³ and Y have the meaning given above), the hydroxymethylene derivatives IV, which may also be in equilibrium with the formyl derivatives V, are first treated with sulfonic acid chlorides such as, B. methanesulfochloride (R '= methyl), trifluoromethanesulfochloride (R' = trifluoromethyl) or p-toluenesulfonyl chloride (R '= p-methylphenyl) in the presence of bases (e.g. triethylamine) to give compounds of the general formula VI. The desired compounds Ib are then obtained by reacting VI with alkyl thiolates Alk S ^- , such as. B. sodium methylate.

The preparation of the compounds of general formula Ic (R¹ = alkylamino or dialkylamino, X = CH, R², R³ and Y have the above Significance) is carried out by reacting the hydroxymethylene derivatives IV can also be in equilibrium with V, with primary or secondary Amines. Alternatively, the alkali salts of IV with the hydrochlorides of primary or secondary amines with release of Sodium chloride are implemented (cf. Ann. Chim. [10] 18 [1932] 103).

Compounds of the formula Ic are also obtained if the ortho-substituted ones Phenylacetic ester of the general formula III with dialkylformamide dialylacetals or with aminal alkyl esters optionally under p-toluenesulfonic acid catalysis (see, for example, Chem. Ber. 97 [1964] 3396).

The new compounds of the general formula Id (R¹ = alkyl, X = CH, R², R³ and Y have the meaning given above) can be prepared, by using an alpha-keto-carboxylic acid ester of the general formula II in a Wittig reaction with an alkyltriphenylphosphonium bromide in Presence of a base (e.g. n-butyllithium, sodium methylate, potassium tert.- butoxide or sodium hydride) in an inert solvent (e.g. diethyl ether, Tetrahydrofuran, dimethylformamide, dimethyl sulfoxide) (cf. also Methods of Organic Chemistry, Volume E1, p. 710, Thieme, Stuttgart 1982).

The alpha-ketocarboxylic acid esters of the general formula II are new. they can e.g. B. by implementing the corresponding aromatic Grignard Compound VII can be prepared with imidazolides of the formula VIII (J. Org. Chem. 46 [1981] 211). R², R³ and Y have the above Importance.

The new compounds of the general formula Ie (R¹ = alkoxy, X = N, R², R³ and Y have the meaning given above) are obtained in that the alpha-ketocarboxylic acid esters II with an O-alkyl substituted Hydroxylamine hydrochloride in the presence of a base (e.g. sodium carbonate, Sodium acetate) in an inert solvent (e.g. methanol). The Compounds of the formula Ie are also obtained if the alpha-ketocarboxylic acid esters II first reacted with hydroxylamine and the resulting Then oximes with alkylating agents of the formula Alk-L (L = halogen, e.g. B. Cl, Br, J) to react.  

A manufacturing process for ortho-substituted phenol ethers general formula If (R¹ = alkylamine or dialkylamino, X = N, R², R³ and Y have the meaning given above) is z. B. the following: Alpha-ketocarboxylic acid esters of the formula II are substituted Hydrazines in the presence of a protonic acid (e.g. hydrochloric acid) in one suitable solvent (e.g. methanol) (cf. Liebigs Ann. Chem. 722 [1969] 29).

The preparation of the ortho-substituted compounds required as starting compounds Phenylacetic ester III takes place, for. B. by alkylation of ortho-hydroxy-phenylacetic acid methyl ester

with omega-aryloxyalkyl halides

R³-Y halogen

according to known methods (methods of organic chemistry, Volume 6/3, p. 54, Thieme, Stuttgart, 1965). You get the same way from ortho-hydroxyphenyl bromide

and omega-aryloxyalkyl halides

R³-Y halogen

ortho-substituted phenyl bromides

which are required according to standard methods for the starting compounds Grignard compounds VII are further implemented.

Omega aryloxyalkyl halides R³-Y-halogen are known compounds or can be easily prepared by known methods, e.g. B. by Monoalkylation of phenols with aliphatic dihaloalkanes (e.g. 1,2-dibromomethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopropane, 1,6-dibromohexane, 1,7-dibromoheptane).

The new compounds of formula I fall due to their manufacture the C = C or C = N double bond in part as an E / Z isomer mixture. These can be done in the usual way, e.g. B. by crystallization or Chromatography, into which the individual components are separated. Both the individual isomeric compounds as well as their mixtures are derived from the Invention includes.

The following example is intended to explain the production of the new active ingredients.

Regulation 1 Methyl 2- (4-phenoxy-butanyl-1-oxy) phenylacetate

28.2 g (0.17 mol) of methyl 2-hydroxyphenylacetate, 25.8 g (0.19 mol) Potassium carbonate and 38.9 g (0.17 mol) of 4-phenoxybutyl bromide Stirred for 24 hours in 400 ml of dimethylformamide at 70 ° C. Then will the solvent was stripped off and the residue was taken up in diethyl ether. It is extracted several times with water and saturated sodium carbonate solution and dries the organic phase over MgSO₄. That after removing the Oil obtained solvent is by chromatography on silica gel (Cyclohexane / ethyl acetate) cleaned. Yield: 31 g (58%).

Regulation 2 alpha- [2- (4-phenoxy-butanyl-1-oxy) phenyl] - β -hydroxyacrylic acid methyl ester

A mixture of 30 g (0.10 mol) of methyl 2- (4-phenoxy-butanyl-1-oxy) phenylacetate is added dropwise to a suspension of 3.4 g (0.14 mol) of sodium hydride in 50 ml of diethyl ether at room temperature. 12.5 g (0.21 mol) methyl formate and 100 ml diethyl ether. The mixture is stirred for 12 hours at room temperature and then hydrolyzed by adding ice. The aqueous, alkaline phase is extracted with diethyl ether, acidified with dil. HCl and shaken out again with diethyl ether. After concentrating the organic phase, 21 g (71%) of alpha- [2- (4-phenoxy-butanyl-1-oxy) phenyl] - β -hydroxyacrylic acid methyl ester are obtained.

Example 1 alpha- [2- (4-phenoxy-butanyl-1-oxy) phenyl] - β- methoxyacrylic acid methyl ester

20 g (0.06 mol) of the compound obtained above together with 7.4 g (0.06 mol) dimethyl sulfate and 8.0 g (0.06 mol) potassium carbonate for 48 hours stirred in 150 ml acetone at room temperature. Then from The precipitate is filtered off, the acetone is drawn off and the residue is in Diethyl ether added. The organic phase is semi-concentrated Washed ammonia and water, dried and concentrated. 15.2 g are obtained (73%) of the title compound as a pure E isomer in the form of colorless Crystals of melting point 88 ° C (compound no. 97).

The following connections can be made in a corresponding manner:  

Table 1

Table 2

Table 3

NMR data of selected compounds from Tables 1 and 2. The chemical shift ( δ ) is given in ppm relative to tetramethylsilane. CDCl₃ serves as solvent.

Compound No. 68
2.17 (q, 2H); 3.60 (s, 3H); 3.71 (s, 3H); 4.11 (m, 4H); 7.08 (m, 9H); 7.47 (s, 1H).

Compound No. 97
2.88 (m, 4H); 3.68 (s, 3H); 3.77 (s, 3H); 4.00 (m, 4H); 7.08 (m, 9H); 7.48 (s, 1H).

Compound No. 140
1.63 (m, 2H); 2.85 (m, 4H); 3.66 (s, 3H), 3.80 (s, 3H); 3.98 (t, 2H); 4.05 (t, 2H); 7.12 (m, 8H); 7.50 (s, 1H).

Compound No. 163
1.50 (m, 4H)); 1.75 (m, 4H); 3.67 (s, 3H); 3.78 (s, 3H); 3.94 (t, 2H); 4.03 (t, 2H); 7.12 (m, 8H)); 7.49 (s, 1H).

Compound No. 195
1.41 (m, 6H); 1.75 (m, 4H); 2.28 (s, 3H); 4.68 (s, 3H); 4.80 (s, 3H); 4.90 (t, 2H); 4.93 (t, 2H); 7.00 (m, 8H); 7.48 (s, 1H).

Generally speaking, the new compounds are characterized by a excellent effectiveness against a wide range of phytopathogenic agents Mushrooms, in particular from the classes of the Ascomycetes and Basidiomycetes, out. They are partially systematically effective and can be used as leaf and Soil fungicides are used.

The fungicidal compounds are particularly interesting for combating a variety of fungi on different crops or their Seeds, especially wheat, rye, barley, oats, rice, corn, lawn, Cotton, soy, coffee, sugar cane, fruit and ornamental plants in horticulture, Viticulture and vegetables - such as cucumbers, beans and squashes -.  

The new compounds are particularly suitable for combating the following Plant diseases:

Erysiphe graminis (powdery mildew) in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,
Podosphaera leucotricha on apples,
Uncinula necator on vines,
Puccinia species on cereals,
Rhizoctonia species on cotton and lawn,
Ustilago species on cereals and sugar cane,
Venturia inaequalis (scab) on apples,
Helminthosporium species on cereals,
Septoria nodorum on wheat,
Botrytis cinerea (gray mold) on strawberries, vines,
Cercospora arachidicola on peanuts,
Pseudocercosporella herpotrichoides on wheat, barley,
Pyricularia oryzae on rice,
Phytophthora infestans on potatoes and tomatoes,
Fusarium and Verticillium species on different plants,
Plasmopara viticola on vines,
Alternaria species in vegetables and fruits.

The compounds are applied by treating the plants with the active ingredients sprayed or dusted or the seeds of the plants with the active ingredients treated. It is used before or after infection Plants or seeds through the mushrooms.

The new substances can be converted into the usual formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and Granules. The application forms depend entirely on the purposes: in any case, they should have a fine and even distribution ensure the effective substance. The wording is in manufactured in a known manner, e.g. B. by stretching the active ingredient with Solvents and / or carriers, optionally using Emulsifiers and dispersants, where in the use of Water as a diluent other than organic solvents Auxiliary solvents can be used. As auxiliaries come for it essentially in question: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), Alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. Ethanolamine, dimethylformamide) and water; Carriers like natural Rock flours (e.g. kaolins, clays, talc, chalk) and synthetic Rock flour (e.g. highly disperse silica, silicates); Emulsifier, such as nonionic and anionic emulsifiers (e.g. polyoxyethylene  Fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants, such as lignin, lye and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% active ingredient.

Depending on the type of effect desired, the application rates are between 0.02 and 3 kg of active ingredient or more per hectare. The new compounds can can also be used in material protection, e.g. B. against Paecilomyces variotii.

The agents or the ready-to-use preparations made therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or Granules are used in a known manner, for example by Spraying, atomizing, dusting, scattering, pickling or pouring.

Examples of such preparations are:

• I. 90 parts by weight of compound no. 66 are mixed with 10 parts by weight of N-methyl- α- pyrrolidone and a solution is obtained which is suitable for use in the form of tiny drops.
• II. 20 parts by weight of compound no. 97 are mixed dissolved, the 80 parts by weight of xylene, 10 parts by weight of Addition product of 8 to 10 moles of ethylene oxide with 1 mole Oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt Dodecylbenzenesulfonic acid and 5 parts by weight of the adduct and 40 moles of ethylene oxide with 1 mole of castor oil. Obtained by pouring and finely distributing the solution in water an aqueous dispersion.
• III. 20 parts by weight of compound no. 140 are dissolved in a mixture, that from 40 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 40 moles There is ethylene oxide in 1 mol of castor oil. By pouring and finely distributing the solution in water gives an aqueous Dispersion.
• IV. 20 parts by weight of compound no. 164 are in a mixture dissolved, the 25 parts by weight of cyclohexanol, 65 parts by weight of one Mineral oil fraction with a boiling point of 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole Castor oil is made up. By pouring and finely distributing the Solution in water gives an aqueous dispersion.  
• V. 80 parts by weight of compound no. 163 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene- α- sulfonic acid, 10 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel and ground in a hammer mill. A spray mixture is obtained by finely distributing the mixture in water.
• VI. 3 parts by weight of compound no. 66 are mixed with 97 parts by weight finely divided kaolin mixed intimately. You get this way a dust containing 3% by weight of the active ingredient.
• VII. 30 parts by weight of compound no. 97 are mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight Paraffin oil that is on the surface of this silica gel is sprayed, intimately mixed. You get one in this way Preparation of the active ingredient with good adhesiveness.
• VIII. 40 parts by weight No. 140 with 10 parts by weight Sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water intimately mixed. A stable aqueous dispersion is obtained. By diluting an aqueous dispersion is obtained with water.
• IX. 20 parts by weight of compound no. 163 are mixed with 2 parts by weight Calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight Fatty alcohol polyglycol ether, 2 parts by weight of sodium salt one Phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil intimately mixed. A stable oily dispersion is obtained.

The agents according to the invention can also be used together in these forms of use with other active ingredients, such as. B. herbicides, insecticides, Growth regulators and fungicides, or also with fertilizers are mixed and applied. When mixed with fungicides in many cases the fungicidal activity spectrum is enlarged.

The following list of fungicides with which the compounds of the invention can be combined, the possible combinations explain, but not limit.

Fungicides which are combined with the compounds according to the invention can include:

Sulfur,
Dithiocarbamates and their derivatives, such as
Ferridimethyldithiocarbamate,
Zinc dimethyldithiocarbamate,
Zinc ethylene bisdithiocarbamate,
Manganese ethylene bisdithiocarbamate,
Manganese-zinc-ethylenediamine-bis-dithiocarbamate,
Tetramethylthiuram disulfide,
Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate),
Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate),
Zinc (N, N'-propylene-bis-dithiocarbamate),
N, N'-polypropylene bis (thiocarbamoyl) disulfide;

Nitroderivatives, such as
Dinitro- (1-methylheptyl) phenylcrotonate,
2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate,
2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate;
5-nitro-isophthalic acid di-isopropyl ester,

heterocyclic substances, such as
2-heptadecyl-2-imidazoline acetate,
2,4-dichloro-6- (o-chloroanilino) -s-triazine,
0,0-diethyl phthalimidophosphonothioate,
5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,
2,3-dicyano-1,4-dithioanthraquinone,
2-thio-1,3-dithio- (4,5-b) -quinoxaline,
1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester,
2-methoxycarbonylamino-benzimidazole,
2- (furyl- (2)) - benzimidazole,
2- (thiazolyl- (4)) - benzimidazole,

N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide,
N-trichloromethylthio-tetrahydrophthalimide,
N-trichloromethylthio-phthalimide,

N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenyl-sulfuric acid diamide,
5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,
2-rhodanmethylthiobenzthiazole,
1,4-dichloro-2,5-dimethoxybenzene,
4- (2-chlorophenylhydroazano) -3-methyl-5-isoxazolone,
Pyridine-2-thio-1-oxide,
8-hydroxyquinoline or its copper salt,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,
2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid aniline,
2-methyl-furan-3-carboxylic acid anilide,
2,5-dimethyl-furan-3-carboxylic acid anilide,
2,4,5-trimethyl-furan-3-carboxylic acid anilide,
2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide,
N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide,
2-methylbenzoic acid anilide,
2-iodo-benzoic acid anilide,
N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,
Piperazin-1,4-diylbis- (1- (2,2,2-trichloro-ethyl) -formamide,
1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane,
2,6-dimethyl-N-tridecyl-morpholine or its salts,
2,6-dimethyl-N-cyclodedecyl-morpholine or its salts,
N- [3- (p-tert-butylphenyl) -2-methylpropyl] cis-2,6-dimethylmorpholine,
N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine,
1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-t-riazole
1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole,
N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl-urea,
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, -
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, -
α - (2-chlorophenyl) - α - (4-chlorophenyl) -5-pyrimidine-methanol,
5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine,
Bis- (p-chlorophenyl) -3-pyridinemethanol,
1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene,
1,2-bis (3-methoxycarbonyl-2-thioureido) benzene,

as well as various fungicides, such as
Dodecylguanidine acetate,
3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide,
Hexachlorobenzene,
DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) -alaninate,
DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester,
N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone,
DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester,
5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine,
3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-d-ion,
3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin,
N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, -
2-cyano- [N- (ethylaminocarbonyl) -2-methoxyimino] acetamide,
1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole,
2,4-difluoro- α - (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol,
N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine,
1 - ((bis- (4-Fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

Examples of use

N-tridecyl-2,6-dimethylmorpholine (A) - Known from DE 11 64 152 - used.

Application example 1 Efficacy against Pyrenophora teres

Barley seedlings of the "Igri" variety were grown in the two-leaf stage with aqueous Suspensions containing 80% active ingredient and 20% emulsifier in dry matter contained, sprayed soaking wet. After 24 hours the Plants with a spore suspension of the fungus Pyrenophora teres inoculated and for 48 hours in a climatic chamber with high humidity placed at 18 ° C. The plants were then in the greenhouse at 20-22 ° C and 70% relative humidity for a further 5 days cultured. Then the extent of symptom development was determined.

The result shows that the active ingredients 97, 140 and 164 when used than 0.05% spray liquor show a better fungicidal effect (97%) than the well-known comparative drug A (70%).

Example of use 2 Efficacy against Phytophthora infestans in tomatoes

Leaves of potted plants of the "Large Beef Tomato" variety were included aqueous spray liquor containing 80% active ingredient and 20% emulsifier in the Contained dry substance, sprayed. After 24 hours the leaves were with a zoospore suspension of the fungus Phytophthora infestans infected. The plants were then placed in a water vapor saturated chamber Temperatures between 16 and 18 ° C set. After 6 days she had Disease on the untreated but infected control plants like this strongly developed that assesses the fungicidal effectiveness of the substances could be.

The result shows that the active ingredients 66, 140, 163 and 164 in the Use as a 0.025% spray liquor has a better fungicidal activity (95%) show as the known comparative drug A (55%).  

Example of use 3 Efficacy against Plasmopara viticola

Leaves of pot vines of the "Müller Thurgau" variety were watery Spray liquor, the 80% active ingredient and 20% emulsifier in the dry matter contained, sprayed. To the duration of action of the active ingredients to be able to assess, the plants were dried after the Spray coating set up in the greenhouse for 8 days. Only then were the Leaves with a zoo spore suspension of Plasmopora viticola (Vine peronospora) infected. After that, the vines were first used for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse with temperatures between 20 and set up at 30 ° C. After this time the plants became Acceleration of the sporangia carrier outbreak again for 16 hours in the humid chamber. Then the assessment of the Extent of fungal outbreak on the undersides of the leaves.

The result shows that the active ingredients 66, 97, 140, 163 and 164 in the Use as a 0.05% spray liquor has a better fungicidal activity (97%) show as the known comparative drug A (35%).

Claims (8)

1. Ortho-substituted phenol ethers of the general formula I in which R¹ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or optionally mono- or doubly substituted amino by C₁-C₄-alkyl,
R² is C₁-C₄-alkyl,
R³ means aryloxy, arylthio or arylalkoxy, the aromatic ring optionally being substituted by one or more of the following radicals: halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-alkylthio, C₁-C₂-haloalkyl, aryl , Aryl-C₁-C₂-alkoxy, C₁-C₄-alkylcarbonyl, amino or cyano, nitro which is mono- or doubly substituted by C₁-C₄-alkyl,
X represents CH or N,
Y represents an optionally unsaturated C₂-C₁₂ alkylene radical. 2. A method of combating fungi, characterized in that the fungi or the materials, plants, seeds or the soil threatened by fungal attack with a fungicidally effective amount of an ortho-substituted phenol ether of the general formula I treated in the
R¹ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or optionally mono- or doubly substituted amino by C₁-C₄-alkyl,
R² is C₁-C₄-alkyl,
R³ means aryloxy, arylthio or arylalkoxy, the aromatic ring optionally being substituted by one or more of the following radicals: halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-alkylthio, C₁-C₂-haloalkyl, aryl , Aryl-C₁-C₂-alkoxy, C₁-C₄-alkylcarbonyl, amino or cyano, nitro mono- or doubly substituted by C₁-C₄-alkyl,
X represents CH or N,
Y represents an optionally unsaturated C₂-C₁₂ alkylene radical. 3. Fungicide, comprising an inert carrier and an ortho-substituted phenol ether of the general formula I in the
R¹ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or optionally mono- or doubly substituted amino by C₁-C₄-alkyl,
R² is C₁-C₄-alkyl,
R³ means aryloxy, arylthio or arylalkoxy, the aromatic ring optionally being substituted by one or more of the following radicals: halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-alkylthio, C₁-C₂-haloalkyl, aryl , Aryl-C₁-C₂-alkoxy, C₁-C₄-alkylcarbonyl, amino or cyano, nitro which is mono- or doubly substituted by C₁-C₄-alkyl,
X represents CH or N,
Y represents an optionally unsaturated C₂-C₁₂ alkylene radical. 4. Alpha- [2- (4-phenoxy-butanyl-1-oxy) phenyl] - β- methoxyacrylic acid methyl ester. 5. Alpha [2- (5-o-chlorophenoxy-pentanyl-1-oxy) phenyl] - β- methoxyacrylic acid methyl ester. 6. Alpha- [2- (6-o-chlorophenoxy-hexanyl-1-oxy) phenyl] - β- methoxyacrylic acid methyl ester. 7. Alpha- [2- (3-phenoxypropyl-1-oxy) phenyl] - β- methoxyacrylic acid methyl ester. 8. ortho-substituted phenol ethers of the general formula II, in the
R² is C₁-C₄-alkyl,
R³ means aryloxy, arylthio or arylalkoxy, the aromatic ring optionally being substituted by one or more of the following radicals: halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-alkylthio, C₁-C₂-haloalkyl, aryl , Aryl-C₁-C₂-alkoxy, C₁-C₄-alkylcarbonyl, amino or cyano, nitro mono- or doubly substituted by C₁-C₄-alkyl,
Y represents an optionally unsaturated C₂-C₁₂ alkylene radical.